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Current concentration

In 2009, the CO2 global average concentration in Earth's atmosphere was about 0.0387% by volume, or 387 parts per million by volume (ppmv).[1][2] This is 103 ppmv (36%) above the 1832 antarctic ice core levels of 284 ppmv.[3] There is an annual fluctuation of about 3–9 ppmv which roughly follows the Northern Hemisphere's growing season. The Northern Hemisphere dominates the annual cycle of CO2 concentration because it has much greater land area and plant biomass than the Southern Hemisphere. Concentrations peak in May as the Northern Hemisphere spring greenup begins and reach a minimum in October when the quantity of biomass undergoing photosynthesis is greatest.[4]

Over 95% of total CO2 emissions are non-anthropogenic. For example, the natural decay of organic material in forests and grasslands, such as dead trees, results in the release of about 220 gigatonnes of carbon dioxide every year. In 1997, Indonesian peat fires were estimated to have released between 13% and 40% of the average carbon emissions caused by the burning of fossil fuels around the world in a single year.[6][7][8] The initial carbon dioxide in the atmosphere of the young Earth was produced by volcanic activity, but modern volcanic activity releases only 130 to 230 teragrams (0.13-0.23 gigatonnes or 145 million to 255 million short tons) of carbon dioxide each year,[9] which is less than 1% of the amount released by human activities.[10]

These natural sources are nearly balanced by physical and biological processes, called natural sinks, which remove carbon dioxide from the atmosphere. For example, some carbon dioxide dissolves in sea water, and some is removed by plants during the photosynthesis.

There is a large natural flux of CO2 into and out of the biosphere and oceans. In the pre-industrial era these fluxes were largely in balance. Currently about 57% of human-emitted CO2 is removed by the biosphere and oceans.[11] The ratio of the increase in atmospheric CO2 to emitted CO2 is known as the airborne fraction (Keeling et al., 1995); this varies for short-term averages but is typically about 45% over longer (5 year) periods.

This addition, presently about 3% of annual natural emissions, is sufficient to exceed the balancing effect of sinks. As a result, carbon dioxide has gradually accumulated in the atmosphere, until at present, its concentration is 30% above pre- industrial levels.[13]

Various techniques have been proposed for removing excess carbon dioxide from the atmosphere in carbon dioxide sinks.

Historical variation

CO2 concentrations over the last 400,000 years

The most direct method for measuring atmospheric carbon dioxide concentrations for periods before direct sampling is to measure bubbles of air (fluid or gas inclusions) trapped in the Antarctic or Greenland ice caps. The most widely accepted of such studies come from a variety of Antarctic cores and indicate that atmospheric CO2 levels were about 260 – 280 ppmv immediately before industrial emissions began and did not vary much from this level during the preceding 10,000 years (10 ka).

The longest ice core record comes from East Antarctica, where ice has been sampled to an age of 800 ka.[14] During this time, the atmospheric carbon dioxide concentration has varied by volume between 180 – 210 ppm during ice ages, increasing to 280 – 300 ppm during warmer interglacials.[15][16]

One study disputed the claim of stable CO2 levels during the present interglacial of the last 10 ka. Based on an analysis of fossil leaves, Wagner et al.[17] argued that CO2 levels during the period 7 – 10 ka were significantly higher (~300 ppm) and contained substantial variations that may be correlated to climate variations. Others have disputed such claims, suggesting they are more likely to reflect calibration problems than actual changes in CO2.[18] Relevant to this dispute is the observation that Greenland ice cores often report higher and more variable CO2 values than similar measurements in Antarctica. However, the groups responsible for such measurements (e.g., Smith et al.[19]) believe the variations in Greenland cores result from in situ decomposition of calcium carbonate dust found in the ice. When dust levels in Greenland cores are low, as they nearly always are in Antarctic cores, the researchers report good agreement between Antarctic and Greenland CO2 measurements.

Changes in carbon dioxide during the Phanerozoic (the last 542 million years). The recent period is located on the left-hand side of the plot, and it appears that much of the last 550 million years has experienced carbon dioxide concentrations significantly higher than the present day.

On longer timescales, various proxy measurements have been used to attempt to determine atmospheric carbon dioxide levels millions of years in the past. These include boron and carbonisotope ratios in certain types of marine sediments, and the number of stomata observed on fossil plant leaves. While these measurements give much less precise estimates of carbon dioxide concentration than ice cores, there is evidence for very high CO2 volume concentrations between 200 and 150 Ma of over 3,000 ppm and between 600 and 400 Ma of over 6,000 ppm.[20] On long timescales, atmospheric CO2 content is determined by the balance among geochemical processes including organic carbon burial in sediments, silicate rock weathering, and vulcanism. The net effect of slight imbalances in the carbon cycle over tens to hundreds of millions of years has been to reduce atmospheric CO2. The rates of these processes are extremely slow; hence they are of limited relevance to the atmospheric CO2 response to emissions over the next hundred years. In more recent times, atmospheric CO2 concentration continued to fall after about 60 Ma. About 34 Ma, when the ice sheets of Antarctica started to take their current form near the Eocene-Oligocene extinction event, CO2 has been found to be about 760 ppm,[21] and there is geochemical evidence that volume concentrations were less than 300 ppm by about 20 Ma. Low CO2 concentrations may have been the stimulus that favored the evolution of C4 plants, which increased greatly in abundance between 7 and 5 Ma. Present carbon dioxide levels are likely higher now than at any time during the past 20 Ma[20] and certainly higher than in the last 0.8 Ma.

Relationship with oceanic concentration

The Earth's oceans contain a huge amount of carbon dioxide in the form of bicarbonate and carbonate ions — much more than the amount in the atmosphere. The bicarbonate is produced in reactions between rock, water, and carbon dioxide. One example is the dissolution of calcium carbonate:

CaCO3 + CO2 + H2O ⇌ Ca2+ + 2 HCO3-

Reactions like this tend to buffer changes in atmospheric CO2. Since the right-hand side of the reaction produces an acidic compound, adding CO2 on the left-hand side decreases the pH of sea water. Reactions between carbon dioxide and non-carbonate rocks also add bicarbonate to the seas. This can later undergo the reverse of the above reaction to form carbonate rocks, releasing half of the bicarbonate as CO2. Over hundreds of millions of years this has produced huge quantities of carbonate rocks.

Ultimately, most of the CO2 emitted by human activities will dissolve in the ocean[22], however the rate at which the ocean will take it up in the future is less certain.